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United States Patent |
5,254,635
|
Stevenson
,   et al.
|
October 19, 1993
|
Rubber composition containing dibenzyl thiuram sulfide
Abstract
A dibenzylthiuram sulphid such as tetrabenzylthiuram disulphide is combined
with a dihydrocarbyl xanthogen polysulphide and/or a xanthate to provide a
composition which has good properties as an accelerator in rubber
vulcanisation, without providing harmful nitrosatables.
Inventors:
|
Stevenson; Arthur (West Bromwich, GB2);
Virdi; Ranvir S. (Handsworth Wood, GB2)
|
Assignee:
|
Robinson Brothers Limited (West Bromwich, GB2)
|
Appl. No.:
|
566838 |
Filed:
|
August 13, 1990 |
Foreign Application Priority Data
| Aug 18, 1989[GB] | 8918890.8 |
| Nov 10, 1989[GB] | 8925415.5 |
Current U.S. Class: |
525/332.7; 525/331.1; 525/331.8 |
Intern'l Class: |
C08C 019/22; C08C 019/20 |
Field of Search: |
525/332.5,332.6,332.7,331.1,331.8
|
References Cited
U.S. Patent Documents
1634924 | Jul., 1927 | Whitby.
| |
2374385 | Apr., 1945 | Sauser.
| |
2453689 | Nov., 1948 | Beaver.
| |
4695609 | Sep., 1987 | Stevenson | 525/352.
|
Foreign Patent Documents |
0184301 | Jun., 1986 | EP.
| |
0283552 | Sep., 1988 | EP.
| |
0284649 | Oct., 1988 | EP.
| |
0284650 | Oct., 1988 | EP.
| |
Other References
Perkacit DP-TB.sub.z TD by AKZO (excerpts).
Seeberger, D. B., A New Safe Thiuram TB.sub.z TD, 1989 Oct. (excerpts).
EPO Search Report of May 15, 1990 in U.K. Patent Application 8918890.
|
Primary Examiner: Henderson; Christopher
Attorney, Agent or Firm: Parmelee, Bollinger & Bramblett
Claims
What is claimed is:
1. A sulfur free vulcanizable composition which comprises 100 part by
weight rubber and accelerators consisting essentially of a dibenzylthiuram
sulfide in an amount up to about 1.5 parts by weight, from about 1 to
about 6 parts by weight dihydrocarbyl xanthogen polysulfide of the formula
R.sup.1 O-CS-S.sub.X -SC-OR.sup.2 wherein R.sup.1 and R.sup.2 are the same
or different and selected from the group consisting of alkyl, cycloalkyl
and N-free heterocyclic groups and x is an integer of at least 2; from
about 0 to about 5 parts by weight of a xanthate compound selected from
the group consisting of dihydrocarbyl xanthates and metal
hydrocarbylxanthates of the formula R.sup.4 O--CS--S--R.sup.5 wherein
R.sup.4 is selected from the group consisting of alkyl, cycloalkyl and
N-free heterocyclic groups and R.sup.5 is selected from the group
consisting of a metal and R.sup.4 ; and less than 0.2 parts by weight of
nitrosatable materials.
2. A composition according to claim 1, wherein the rubber is in latex form.
3. A compositon according to claim 1, which comprises from 0.5 to 4 parts
by weight of said dihydrocarbyl xanthogen polysulfide.
4. A composition according to claim 3, which comprises from 2 to 4 parts by
weight of said dihydrocarbyl xanthogen polysulfide.
5. A composition to claim 1, wherein said dibenzylthiuram sulfide is
tetrabenzylthiuram monosulfide.
6. A composition according to claim 1, wherein said dibenzylthiuram sulfide
is a dibenzylthiuram polysulfide.
7. A composition according to claim 6, wherein said dibenzylthiuram
polysulfide is tetrabenzylthiuram disulfide.
8. A composition according to claim 1, which comprises 0.1 to 1 part by
weight of said dibenzylthiuram sulfide per part by weight of said
dihydrocarbyl xanthogen polysulfide.
Description
The present invention relates to new rubber products and to systems for use
in curing rubber.
Commercial rubber goods generally include nitrogen-containing materials
which are used as, or formed from, curing or accelerating agents
Dithiocarbamates, e.g. of the formula (R.sub.a R.sub.b N-CSS).sub.y M, and
thiuram sulphides, e.g. of the formula R.sub.1 R.sub.b N-CS-S.sub.z
-CS-NR.sub.a R.sub.b, in which y and z are each integers, R.sub.a and
R.sub.b are each aryl, alkyl or substituted alkyl and M is a metal such as
sodium or zinc, are widely used as accelerators and curing agents for
rubber goods. N-nitrosamines of the formula R.sub.a R.sub.b NNO are known
to be present in, and formed from, corresponding dithiocarbamates and
thiuram sulphides Other N-containing compounds used in rubber processing,
e.g. sulphenamides and thioureas, can also give N-nitrosamines
(hereinafter referred to simply as "nitrosamines").
EPDM (ethylene-propylene-diene-modified) rubber is conventionally cured
using a combination of dipentamethylenethiuram hexasulphide,
tetramethylthiuram disulphide (TMTD) and tellurium diethyldithiocarbamate.
Neoprene is conventionally cured using zinc oxide activated with a
thiourea (e.g. ethylenethiourea or diethylthiourea) or a tertiary amine
(e.g. hexamethylenetetramine). The given N-containing activators/curing
agents are all nitrosatables.
Nitrosamines are recognised to be carcinogenic in animals, birds and fish.
Among those nitrosamines tested, only those with exceptional structures,
e.g. where R.sub.a or R.sub.b is a tertiary group, or R.sub.a and R.sub.b
are each benzyl, have been found to lack carcinogenic activity; see
Druckrey et al, Zeitschrift fuer Krebsforschung 69 (1967) 103-201 and
Lijins et al, J. Nat. Cancer Inst. 49 (1972) 1329-1249. Nitrosamines in
which R.sub.a and R.sub.b are each methyl, ethyl, propyl or butyl groups,
or R.sub.a and R.sub.b together represent the pentamethylene group, are
particularly potent.
Nitrosamines are of potential danger wherever they can come into contact
with foodstuffs or sensitive skin, or wherever they can build up in a
closed atmosphere, e.g. in underwater environments, diving gear or parked
cars. There is a risk of exposure to nitrosamines during the manufacture
of dithiocarbamates and related compounds, and during their use in
manufacturing rubber goods. The presence of nitrosamines in rubber goods
is potentially of risk to humans.
Rubber of the type used for baby teats and soothers typically has a
nitrosamine content of about 0.5 ppm. Very careful formulation and washing
is needed to reduce this concentration to an acceptable level for babies,
i.e. below 0.01 ppm. However, because dithiocarbamate accelerators and
related compounds are usually used in amounts of up to 1% by weight of
rubber, there remains, after curing and washing, a substantial residue of
N-containing material capable of nitrosation by nitrite in saliva.
The attention paid to TMTD in rubber vulcanisation probably outweighs that
paid to any other accelerator, mainly because TMTD will vulcanise
elastomers without additional elemental sulphur When used as a vulcanising
agent in rubbers, it imparts a high resistance to thermal ageing. TMTD is
regarded as the most active of the thiurams (including TMT monosulphide)
but gives adverse effects in working environments.
The BRMA Code of Practice for Toxicity and Safe Handling of Rubber
Chemicals (1985) reported that prolonged exposure to TMTD has been
associated with the development of chronic conjunctivitis, although TMTD
is not regarded as an acute eye irritant. It reacts with nitrite to
produce carcinogenic N-nitrosodimethylamine and is known to be most toxic
of the thiurams. If absorbed by humans before or after consumption of
alcohol it can give rise to unpleasant side-effects (for example vomiting,
flushing, etc). It is also listed by the International Contact Dermatitis
Group for routine skin patch testing in appropriate circumstances.
An effective, safe substitute for TMTD is required. A relatively harmless
compound, such as a tetrabenzylthiuram sulphide (hereinafter "TBS"), is
generally a poor accelerator (see Example 2, below). A TBS may also bloom,
although tetrabenzylthiuram disulphide and tetrabenzylthiuram
tetrasulphide have variously been proposed as vulcanisation accelerators
and for hindering bloom, in EP-A-0283552, EP-A-0284649 and EP-A-0284650.
U.S. Pat. No. 1,634,924, U.S. Pat. No. 2,374,385 and U.S. Pat. No.
2,453,689 each disclose the use of dihydrocarbyl xanthogen polysulphides
as accelerators in rubber compositions. For best results, a nitrosatable
component is also present. In a single instance in U.S. Pat No. 1634924
(Example VIII), no amine is used, but the state of cure is relatively very
poor. In U.S. Pat. No. 2453689, the highest recorded tensile strength is
2700 lb/in.sup.2 (18.6 MPa). This is insufficient for practical utility.
Perhaps for this reason, xanthogen polysulphides appear not to have been
used on any commercial scale, over the last 50 years.
Xanthogen disulphides are used as chain-length modifiers in, for example,
emulsion polymerisation processes, and have been proposed as accelerators,
almost always in combination with an activator such as dibenzylamine.
Known accelerators for use in rubber compositions include xanthates,
usually in conjunction with an amine activator.
EP-A-0184301 discloses a composition, suitable for use as an accelerator in
rubber curing processes, that comprises a mixture of two active
components, i.e. a dihydrocarbyl xanthogen polysulphide and a xanthate
selected from metal hydrocarbylxanthates and dihydrocarbylxanthates, at a
respective weight ratio of 600:1 to 0.2:1. EP-A-0184301 also discloses
vulcanisable compositions that comprise 100 parts by weight rubber; 1 to 6
parts by weight of a dihydrocarbyl xanthogen polysulphide; 0.01 to 5 parts
by weight of a xanthate as defined above; sulphur; and less than 0.4 part
by weight of nitrosatable materials (including compounds which are
converted to nitrosatables under vulcanisation conditions).
A first object of the present invention is to reduce the environmental
problems associated with commercial rubber processing and rubber products.
A second object is to provide rubber compositions which cure
satisfactorily in the presence of as little as possible (and preferably in
the absence) of dangerous N-containing materials such as nitrosatables,
including tertiary and, especially, secondary amines.
It has now been discovered that the addition of one or more dibenzylthiuram
sulphides such as TBS compounds to either or both of the two active
components described in EP-A-0184301 is desirable. In particular, the
combination of the hydrocarbyl xanthogen polysulphide and TBS has
unexpected advantages. The xanthate may also be present, and the xanthate
and TBS may be combined as a commercial product, for addition to the
dihydrocarbyl xanthogen polysulphide.
Combinations as described may be added to polymers to form a vulcanisable
composition which can be vulcanised (e.g. as described in EP-A-0184301) to
give any appropriate article. The processing safety and cure rate are
unexpectedly increased, and the final state of cure enhanced. The final
torque cure curve (rheometer) may be almost ideal for products such as
moulded baby teats.
An article of the invention as defined above or obtained by vulcanisation
in accordance with the invention may be shaped in a form intended for or
adapted to skin contact. The article may be used by insertion into the
mouth, for example, a mouthpiece for use in anaesthesia or oxygen supply
in atmospheres of low or nil oxygen content, e.g. an underwater
environment. The article may be a baby product such as a teat, soother or
dummy. Further examples of articles of the invention (which may contact
skin) are goggles, skin-diving suits, gloves (including surgical gloves),
surgical rubbers, contraceptives, balloons and furnishings.
The article may be an automobile component, e.g. a tire. An article
potentially of particular value is an aircraft tire, owing to the fact
that the invention provide vulcanised natural rubber articles free or
substantially free of undesirable nitrosatables during both manufacture
and use, and also because reversion can be low or non-existent. In
general, a vehicle may comprise an article of the invention, whether as a
tire or as an item of furnishing.
The use of xanthogen polysulphide curing agents can generally obviate the
need for secondary amine-based accelerators, but vulcanising agents based
on dibenzylamine can be considered as precursors of N-nitrosodibenzylamine
which has been shown to have very low carcinogenic activity when fed to
rats (see Druckrey et al, supra).
The content of harmful nitrosatables in a composition or product of the
invention is preferably as low as possible. Especially when natural rubber
is used, the level of harmful material is preferably no more than 0.1,
more preferably no more that 0.01 and most preferably no more than 0.001
ppm, with reference to either article or composition. By careful choice of
constituents and reactants, an article of the invention can have such
characteristics.
The use of N-containing materials other than those based on dibenzylamine,
such as secondary and tertiary amines, is not inevitably excluded from the
present invention; in certain circumstances, the use of such compounds
appears to be necessary in order to provide a satisfactory degree of cure,
especially when the rubber is a synthetic rubber. Nevertheless, the level
of such materials, according to the present invention, is considerably
lower than has previously been used commercially, and this represents a
major technical advance. There is less than 0.4, preferably less than 0.3,
more preferably less than 0.2, and most preferably less than 0.1, part
nitrosatables. These FIGURES are expressed in parts by weight per 100
parts by weight of rubber.
The dibenzylthiuram sulphide used in the present invention is preferably a
TBS but may also be a salt of the formula M[--(S).sub.m --CS--N(Bz).sub.2
].sub.n wherein Bz indicates benzyl, m is an integer, e.g. 1 or 2, and M
is a metal such as zinc or another transition metal and n is its valency
(preferably 2).
The present invention is based on the combined utility of the
dibenzylthiuram sulphide and a dihydrocarbyl (by "hydrocarbyl", we include
substituted hydrocarbyl) xanthogen polysulphides as rubber-curing agents.
The xanthogen polysulphides may have the formula R.sup.1 O--CS--S.sub.x
--CS--OR.sup.2 wherein R.sup.1 and R.sup.2 are the same or different and
are each alkyl, cycloalkyl or N-free heterocyclic groups optionally
substituted by substituents which either do not contain nitrogen or do not
give rise to nitrosatable amines, and x is at least 2, and often greater
than 2, e.g. 4 or 5. The maximum number of carbon atoms in R.sup.1 or
R.sup.2, and preferably both, is usually about 20. R.sup.1 and R.sup.2 are
preferably each C.sub.1-6 alkyl and are usually the same, e.g. isopropyl.
A xanthogen polysulphide of the given formula can be prepared by reacting
the corresponding xanthogen disulphide with sulphur or by reacting a
xanthate salt, e.g. of the formula R.sup.1 O--CS--S--Na, with a sulphur
halide, e.g. S.sub.2 Cl.sub.2. It is known in the art that the products of
these reactions are mixtures of compounds in which x is 3, 4, 5 or higher;
when the product is analysed the value of x is not necessarily integral,
but the components of the mixture can be separated at least partially by
chromatographic techniques. x is often at least 3, e.g. about 4.
The amount of the curing agent as defined above, for vulcanisation, is
usually at least 0.5 or 1, preferably at least 1.5, e.g. up to 4 or 6, and
most preferably 2 to 4, parts by weight per 100 parts by weight of rubber.
The curing agent can be formulated with rubber and any other conventional
components which may be needed, to form a vulcanisable composition which
is then vulcanised. The vulcanisable composition may include sulphur, e.g.
in an amount of up to 2 parts by weight per 100 parts by weight of the
rubber. The temperature of vulcanisation of a dry rubber composition is
preferably at least 130.degree. C., e.g. 140.degree. to 180.degree. C. The
vulcanisation temperature is usually 35.degree. to 100.degree. C. for a
latex. The composition may be formed, before, during or after curing, into
a desired article, e.g. via an intermediate sheet form.
It is often desirable, on economic grounds, that the speed of vulcanisation
of a cure system used in the invention should be increased by the use of
activators. Activators which work satisfactorily with the curing agents of
the invention are primary amines and also their sulphonated derivatives
(sulphenamides), but it should be noted that sulphenamides are
nitrosatable. A suitable primary amine has the formula R.sup.3 NH.sub.2
wherein R.sup.3 is as defined above for R.sup.1.
As indicated in EP-A-0184301, xanthates are especially good activators for
xanthogen polysulphides. Examples are dihydrocarbyl xanthates and metal
hydrocarbylxanthates, e.g. of the formula R.sup.4 O--CS--S--R.sup.5
wherein R.sup.4 is of the same scope as R.sup.1 and R.sup.5 is a metal or
a group of the same scope as R.sup.1 (in the latter case, R.sup.4 and
R.sup.5 may be different or, more often, the same); specific examples are
zinc isopropylxanthate and dibutyl xanthate. The metal
hydrocarbylxanthates are often preferred. The amount of xanthate with
respect to rubber may be 0.01 to 5 pphr; it need be no more than 0.05
pphr.
The amount of TBS (often the disulphide) is preferably 0.1 to 1 or even
1.5, e.g. 0.2 to 0.7, parts per part dihydrocarbyl xanthogen polysulphide,
e.g. diisopropyl xanthogen tetrasulphide. An amount less than 0.1 part has
reduced effect; more than 1.5 part increases the likelihood of blooming.
In a rubber/polymer composition, the loading of each of these components
will not usually exceed 2.5 pphr, although the amounts given above may
also be applicable.
The rubber which is used will be chosen as necessary. It may be in latex or
dry form. Natural, Hypalon, SBR, neoprene, butyl, EPDM and nitrile rubbers
may be used. Pre-cure and post-cure natural rubber latices are suitable
for forming babies' bottle teats. Dry natural rubber or synthetic
polyisoprene is preferred for moulded baby teats.
A composition of the invention may include conventional rubber processing
additives and components such as fillers, processing aids and
anti-oxidants. Carbon black, for example, may be used in an amount of 25
to 400 pphr. A conventional inorganic activator which may be used is zinc
oxide. A conventional organic activator and processing acid which may be
used is stearic acid. Another known processing aid which may be used
comprises a paraffinic processing oil. An anti-oxidant should not be
nitrosatable; a phenol such as 2,
2'-methylenebis[5-(1-methylcyclohexyl)-p-cresol]or Antioxidant 2246, i.e.
2, 2'-methylenebis(4-methyl-6-tert-butylphenol), can be used.
The following Examples 4 to 6, 8, 12 and 13 illustrate the invention.
Examples 1 to 3, 7 and 9 to 11 are comparative. All amounts are in parts
by weight. The following abbreviations are used:
______________________________________
TMTD tetramethylthiuram disulphide
TBzTM tetrabenzylthiuram monosulphide
TBzTD tetrabenzylthiuram disulphide
DIXT diisopropyl xanthogen polysulphide
(principally the tetrasulphide)
ZIX zinc isopropylxanthate
ZBeD zinc dibenzylthiuram disulphide
______________________________________
EXAMPLES 1 TO 4 (SULPHER-FREE)
The following base mix was prepared in a 3A Banbury mixer:
______________________________________
Natural rubber (SMR)
100
Zinc oxide 5
Stearic acid 1
Antioxidant (Nonox WSL)
1
Carbon black 5
CaCO.sub.3 50
______________________________________
Portions of this were taken, and the following additions were made in a
2-roll mill:
______________________________________
Example 1 2 3 4
______________________________________
TMTD 3.0 -- -- --
TBzTD -- 3.0 -- 1.5
DIXT -- -- 3.0 1.5
______________________________________
EXAMPLES 5 AND 6
Portions of the base mix used in Examples 1 to 4 were taken and, again in a
2-roll mill, 0.75 parts TBzTM (Ex. 5) or TBzTD (Ex. 6) were added in
addition to 0.75 parts DIXT and 1.6 parts sulphur.
EXAMPLES 7 TO 13 (BABY TEAT FORMULATIONS)
The following base mix was prepared on a 406 mm (16 inch) 2-roll mill:
______________________________________
Premasticated pale crepe
100
Antioxidant 2246 1.0
Stearic acid 0.8
Zinc carbonate 1.5
Sulphur 2.0
______________________________________
Portions were taken, and the following additions were made on the mill:
______________________________________
Example 7 8 9 10 11 12 13
______________________________________
DIXT 1.5 1.5 -- -- 1.5 1.5 1.5
ZIX -- -- -- -- 0.016 0.016
0.016
TBzTD -- 0.5 0.5 1.5 -- 0.5 --
ZBeD -- -- -- -- -- -- 0.5
______________________________________
Rheological study of all the above formulations was carried out using a
Monsanto Rheometer 100S linked to a data unit and a chart recorder.
Appropriate test pieces were moulded for tensile strength and elongation
(before and after ageing), all to BS 903.
Mooney viscosities and scorch time determination were carried out at
120.degree. C. by using a large rotor on a SPRI (Negretti Automation)
pneumatically-operated Mooney Viscometer.
Physical tests (moduli at various elongations, tensile strength
measurements and elongation at break) were carried out using a Lhomme and
Argy tensile testing machine.
Ageing studies (ageing in air) were carried out in Wallace cell ovens for
70 hours at 100.degree. C.
The results are tabulated below. In the Table, the following abbreviations
apply:
______________________________________
Vulcanisation Data:
T.sub.50 time to 50% cure (min)
T.sub.90 time to 90% cure (min)
M.sub.H maximum torque
R.sub.H highest cure rate
Mooney Process Data at 120.degree. C.:
t.sub.5 time to 5 point rise (min)
t.sub.10 time to 10 point rise (min)
t.sub.35 time to 35 point rise (min)
Physical Properties before and after ageing:
T.sub.b tensile strength before ageing (MPa)
E.sub.b elongation at break before ageing (%)
.DELTA.T.sub.b
tensile strength change after ageing (MPa)
.DELTA.E elongation change after ageing (%)
______________________________________
Comparison of the T.sub.50 /T.sub.90 data for Examples 1, 2 and 3 shows
that, compared to TMTD, DIXT and, especially, TBzTD are poor accelerators
in sulphur-free systems. However, the combinat-ion of TBzTD and DIXT
(Example 4; total weight of accelerator still 3 pphr) gives similar
results to those for TMTD, both as an accelerator and in the scorch data
(t.sub.5, t.sub.10, t.sub.35). The ageing characteristics for Example 4
are satisfactory. For the sulphur-containing formulations, Examples 5 and
6 show that when the monosulphide is tested alongside the disulphide, it
shows comparable performance when both are used in conjunction with DIXT.
For subsequent Examples, visual inspection of the rheographs show that the
scorch time of the DIXT cure system (Example 7) is increased when TBzTD is
included (Example 8) in the curative system. This is further supported by
the Mooney process data at 120.degree. C. The cure rate and maximum torque
given by R.sub.H and M.sub.H respectively are also increased, indicating
enhanced cross-linked density of the rubber. TBzTD alone (Examples 9, 10)
is seen to be slow in curing, and can be classified as a relatively
inactive accelerator. Combinations of DIXT and TBzTD (Example 8) produce
vulcanisates of superior physical properties and good transparency, and
are free from odour or taste. The ageing properties of the combination are
relatively good.
Further, comparison of Examples 11, 12 and 13 shows that the scorch time
given by the cure composition of a xanthogen polysulphide (DIXT) and a
metal xanthate (ZIX), as in Example 11, is noticably reduced in the
presence of ZBeD (Example 13) and increased in the presence of TBzTD
(Example 12). This is strongly supported by the Mooney T process data at
120.degree. C. T.sub.90 is reduced with ZBeD and increased with TBzTD in
the presence of a DIXT/ZIX/S cure composition. The tensile strength of a
cure composition containing DIXT/ZIX/S (Example 12) in the presence of
TBzTD increased with respect to Example 11 but, for ZBed (Example 13), a
decrease was obtained. Therefore, the most useful "safe" accelerator which
will improve the sulphur cross-links of rubber vulcanisates in the
presence of DIXT/ZIX/S, and produce good physical properties, is TBzTD.
TABLE
__________________________________________________________________________
Example
T.sub.50
T.sub.90
M.sub.H
R.sub.H
t.sub.5
t.sub.10
t.sub.35
T.sub.b
E.sub.b
.DELTA.T.sub.b
.DELTA.E
__________________________________________________________________________
1 3.26
7.28
45.1
0.19
11 13 16 23.6
700
-6.7
-20
2 4.52
9.31
16.4
0.04
21 25 31 8.3
840
-6.6
-95
3 2.34
4.52
27.4
0.19
9 10 11 14.7
890
-14.7
-240
4 3.27
6.21
38.8
0.4
11 13 16 21.3
750
-11.6
-55
5 3.03
3.24
31.9
0.75
-- -- -- -- -- -- --
6 3.06
3.28
21.8
0.68
-- -- -- -- -- -- --
7 4.39
5.31
33.0
0.34
12.5
13 -- 12.6
920
-5.8
-20
8 5.54
6.46
41.4
0.43
13 14 -- 18 840
-0.3
-340
9 9.08
11.58
30.0
0.09
26.5
30 -- 11.6
950
-1.4
-310
10 8.47
10.35
38.1
0.14
22 24.5
-- 14.9
850
-1.8
-300
11 3.0
3.2
40.8
1.05
10.25
10.5
-- 20.3
850
-1.6
-50
12 3.4
4.0
47.6
1.34
14.5
15 -- 21.9
750
-2.9
-110
13 2.09
2.33
47.3
1.28
5.5
6 -- 15.5
760
-3.8
-160
__________________________________________________________________________
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